Hybrid polyurethane spray foams made with urethane prepolymers and rheology modifiers

ABSTRACT

Hybrid spray foams utilize a urethane reactant, a crosslinker, and an (optional) epoxy and/or acrylic resin along with a blowing agent and rheology modifier to produce a quick-setting foam that remains in place until the foam forms and cures. The urethane reactant may be formed as an adduct with or without the use of isocyanate chemistry. In some embodiments, the polyurethane oligomer is made by reacting cyclocarbonates and di- or polyamines, while in other embodiments the polyurethane backbone employs the use of commercially available capped or blocked urethane oligomers made by any method. The oligomers contain reactive groups, typically at the oligomer ends, that crosslink with crosslinkers or with acrylic or epoxy resins to form hybrid polyurethane foams. Foams may also contain a plasticizer, and/or a surfactant as well as other optional additives. Methods of making such foams are also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of prior provisional applicationSer. No. 61/433,561, filed Jan. 18, 2010, the entire content of which isincorporated by reference.

TECHNICAL FIELD

The present invention relates generally to spray foams that are used tofill cavities, cracks, and crevices to enhance the sealing andinsulating properties of buildings and, more particularly, touser-friendly spray foams based on urethane oligomers or prepolymersthat avoid hazardous monomeric isocyanates. In most embodiments, rapidlycrosslinking film-forming polymers are used and rheology modifiers areincorporated to resist mobility of the composition while allowing it tofoam and cure.

BACKGROUND OF THE INVENTION

Spray foams have found widespread utility in the fields of insulationand structural reinforcement. For example, spray foams are commonly usedto insulate or impart structural strength to items such as automobiles,hot tubs, refrigerators, boats, and building structures. In addition,spray foams are used in applications such as cushioning for furnitureand bedding, padding for underlying carpets, acoustic materials, textilelaminates, and energy absorbing materials. Typically, spray foams,especially those used as insulators or sealants for home walls, arepolyurethane spray foams.

Polyurethane spray foams and their methods of manufacture are wellknown. Typically, polyurethane spray foams are formed from two separatecomponents, commonly referred to as an “A” side and a “B” side, thatreact when they come into contact with each other. In traditionalpolyurethane foams, the first component, or the “A” side, contains anisocyanate such as a di- or poly-isocyanate that has a high level ofhighly reactive isocyanate (—N═C═O) functional groups on the molecule.The second component, or “B” side, contains nucleophilic reagents. Othercomponents may include surfactants, blowing agents, catalysts, and/orother auxiliary agents. The nucleophilic reagents are generally polyolshaving two or more hydroxyl groups, primary or secondary polyamines,and/or water. In some cases, mixtures of diols and triols are used toachieve the desired foaming properties. The overall polyol hydroxylnumber is designed to achieve a 1:1 ratio of first component to secondcomponent (A:B). U.S. Pat. No. 5,444,099 to Abe et al., U.S. Pat. No.4,945,120 to Kopp et al. and U.S. Pat. No. 3,984,360 to Galbreath et al.disclose polyurethane spray foams which may be capable of being appliedat low temperatures. The polyurethane foams in each these patentsrequire a polyisocyanate component.

A major problem associated with conventional polyurethane spray foams isthat the first component (the “A” side) typically contains high levelsof hazardous methylene-diphenyl-di-isocyanate (MDI) monomers. When thefoam reactants are sprayed, the MDI monomers form droplets that may beinhaled by workers installing the foam if stringent safety precautionsare not followed. An additional problem with such conventionalpolyurethane spray foams is that residual polymericmethylene-diphenyl-di-isocyanate (PMDI) that is not used is consideredto be a hazardous waste. PMDI typically has an NCO content of about 20%.Therefore, specific procedures must be followed to ensure that the PMDIwaste product is properly and safely disposed of in a licensed landfill. Such precautions are both costly and time consuming.

Attempts have been made to reduce or eliminate the presence ofisocyanate and/or isocyanate emission by spray foams into theatmosphere. For example, latex foams have been used to reduce oreliminate the presence of isocyanate and/or isocyanate emission by sprayfoams. Typical plural component latexes are supplied with a latex resinas the major component in the “A” side and a crosslinking agent as theminor component in the “B” side. The crosslinking agent in the latexspray foams is generally highly reactive. Thus, the crosslinking agentis generally supplied neat (i.e., not in solution). Additionally, thehigh reactivity of the crosslinking agent may reduce the stability andresult in a short shelf life of the foamable material. U.S. PatentPublication Nos. 2008/0161430; 2008/0161431; 2008/0161433; 2008/0161432;2009/0111902; and 2010/0175810 to Korwin-Edson et al. disclose a roomtemperature crosslinked latex foams.

Additionally, attempts have been made to utilize pre-polymerization tolower the concentration of diisocyanate monomers. For example, U.S.Patent Publication No. 2006/0047010 to O'Leary teaches a spraypolyurethane foam that is formed by reacting an isocyanate prepolymercomposition with an isocyanate reactive composition that is encapsulatedin a long-chain, inert polymer composition. The isocyanate prepolymercomposition contains less than about 1 wt % free isocyanate monomers, ablowing agent, and a surfactant. Although these pre-polymers for sprayfoams contain low concentrations of diisocyanate monomers, they stillcontain isocyanate groups. Thus, these foams may be better thanconventional polyurethane foams from a toxicological point of view, butare still considered to be hazardous. In addition, such foams do notsolve the waste problems discussed above. Nor have such foams achievedtoxicological acceptance.

Despite attempts to reduce or eliminate the use of isocyanate in sprayfoams and/or reduce isocyanate emission into the air, there remains aneed in the art for a spray foam that is non-toxic, environmentallyfriendly, and stable over time.

SUMMARY OF THE INVENTION

The spray foams of this invention utilize a urethane oligomer orprepolymer that may be formed as an adduct with or without the use ofisocyanate chemistry. In some embodiments, the polyurethane oligomer ismade by reacting cyclocarbonates and di- or polyamines, while in otherembodiments the polyurethane backbone employs the use of commerciallyavailable capped or blocked urethane oligomers, made by any method. Intwo part (A/B) foams, the oligomers form one component and containreactive groups that crosslink with reactive groups of the othercomponent to form hybrid polyurethane foams. The spray foam alsoincludes a blowing agent(s) to produce the gassing or foaming, and arheology modifier. Foams may also contain a plasticizer, and/or asurfactant as well as other optional additives. Methods of making suchfoams are also provided.

In one aspect, the invention is a spray foam system comprising

a urethane reactant having at least two reactive functional groups otherthan isocyanates, the urethane reactant selected from (a) a preformedurethane prepolymer and (b) a cyclocarbonate and a polyamine that reactin situ to form a urethane prepolymer adduct;

a crosslinker having at least two reactive functional groups adapted tobe rapidly crosslinked with the reactive functional groups of theurethane reactant to form a hybrid polyurethane, optionally with a resinpolymer having further reactive functional groups;

a blowing agent for initiating a foaming reaction; and

a rheology modifier;

wherein the urethane reactant, the crosslinker and the optional resinpolymer are separated into at least two parts on the basis of theirreactive functional groups to prevent premature crosslinking until afoaming reaction is initiated.

As noted above the urethane reactant may comprise a pre-formed urethaneoligomer, or one formed in situ during the foaming reaction. Preformedurethane oligomers include the NIBA type and also IBA types (as definedlater herein) provided the isocyanate ends are capped with otherreactive functionalities like amine or acrylate. Urethane reactants willgenerally have aliphatic or aromatic backbones or a mixture of the two.Polyester and polyether backbones are typical. Preformed urethanereactants include commercially known urethane acrylate oliogomers orUAOs, as well as NIPU-like oligomers formed from cyclocarbonates andamines. Urethane oligomers formed in situ from building blocks includethe cyclocarbonate and polyamine reactants, although heat must generallybe supplied for this reaction to proceed quickly enough for the rapidtack-free cures required in the building industry. Heat may be suppliedexternally or by internal heat of chemical reactions, such as heatgenerated by the addition of acrylic monomers and polyamines.

Thus, in some embodiments, the compositions further comprises optionalacrylate monomers, or optional resin polymers, like epoxy or acrylicresins. These may produce internal heat of reaction as well asparticipate in crosslinking reactions to rapidly form the foams.

The composition further comprises a blowing agent that gives off a gasor expands to fill polymeric cells of the foam. The blowing agent may bea single chemical compound that generates a gas upon heating,irradiation, or photo initiation, two or more chemicals that form a gasupon mixing, or a phase change blowing agent. The blowing agent isgenerally a low-boiling point hydrocarbon or halogenated hydrocarbonlike a fluorocarbon. Some specific fluorocarbon blowing agents includeHFC 245fa and FEA-1100 and mixtures thereof.

In another aspect, the invention relates to a method of sealing,insulating or sealing and insulating part of a building structure,comprising

mixing the at least two parts containing the urethane reactant andcrosslinking components of the spray foam system described above;

applying the mixture to the building structure, thereby permitting theurethane reactant, the crosslinker and optional resin polymer tocrosslink, and

initiating a blowing reaction to form a foamed product,

the rheology modifier holding the mixture in place against the buildingstructure for a time sufficient for the blowing agent to produce athree-dimensional, tack-free foamed product.

In some embodiments, the method may include applying heat to one or moreparts of the spray foam to a temperature above ambient to facilitate thecrosslinking reaction. In some embodiments, the two parts are separatelydelivered to an application device, such as a sprayer or spray gun,mixed in the application device, optionally heated in the spray device,and applied to the building structure from the application device. Whenapplied to vertical surfaces of a building structure, it is importantthat the foams crosslink rapidly so that they withstand the force ofgravity until they become cured. In some embodiments, the foamed productcures to tack-free status in less than about 120 seconds, less than 60seconds, less than 30 seconds or even less than 15 seconds. In someembodiments, the foamed product cures to resilient hardness in less thanabout 20 minutes, less than about 15 minutes, or less than about 10minutes. In some embodiments, the foam system is applied to a seam orcrevice between two structural components, or into a cavity or openspace framed by structural components, or both.

In a third aspect, the invention relates to a hybrid polyurethane foamedproduct made by the process described above using the foam systemdescribed above. Thus, the foamed product is the product of

reacting an optional non-isocyanate reactive functional groups of aurethane reactant with a crosslinker and optionally with a resin polymerin the presence of a rheology modifier under conditions to rapidly formcells of a crosslinked hybrid polyurethane polymer; while initiating ablowing reaction to cause a gas to be disposed within at least some ofthe cells.

In some embodiments, the foamed product has cells are at least 80%closed or an 80% closed cell content; in other embodiments the closedcell content may be greater than 90%. In other embodiments, a more opencell structure is desired and the closed cell content need only be 50%or even less. As with the foam system described above, the resin, whenused, may include epoxy or acrylic functional groups; the backbones maybe aliphatic or aromatic and may include polyether and polyesterbackbones; and the blowing agent may comprise a low-boiling pointhydrocarbon or halogenated hydrocarbon like fluorocarbons.

Various other aspects of this invention will become apparent to thoseskilled in the art from the following detailed description of thepreferred embodiment, when read in light of the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, incorporated herein and forming a part of thespecification, illustrate the present invention in its several aspectsand, together with the description, serve to explain the principles ofthe invention. In the drawings, the thickness of the lines, layers, andregions may be exaggerated for clarity.

FIG. 1 is an illustration depicting the chemical reaction ofcyclocarbonate groups with amine groups to form a non-isocyanatepolyurethane (NIPU) and subsequently reacting the non-isocyanatepolyurethane with epoxy groups to form a hybrid non-isocyanatepolyurethane (HNIPU); and

FIGS. 2A and 2B are illustrations of actual spray foams made and sprayedas described in more detail in the examples.

DETAILED DESCRIPTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the invention belongs. Although any methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the present invention, the preferred methodsand materials are described herein. All references cited herein,including books, journal articles, published U.S. or foreign patentapplications, issued U.S. or foreign patents, and any other references,are each incorporated by reference in their entireties, including alldata, tables, figures, and text presented in the cited references.

Unless otherwise indicated, all numbers expressing ranges of magnitudes,such as angular degrees or web speeds, quantities of ingredients,properties such as molecular weight, reaction conditions, dimensions andso forth as used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessotherwise indicated, the numerical properties set forth in thespecification and claims are approximations that may vary depending onthe desired properties sought to be obtained in embodiments of thepresent invention. Notwithstanding that the numerical ranges andparameters setting forth the broad scope of the invention areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical values, however,inherently contain certain errors necessarily resulting from error foundin their respective measurements. All numerical ranges are understood toinclude all possible incremental sub-ranges within the outer boundariesof the range. Thus, a range of 30 to 90 degrees discloses, for example,35 to 50 degrees, 45 to 85 degrees, and 40 to 80 degrees, etc.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the invention belongs. Although any methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the present invention, the preferred methodsand materials are described herein. All references cited herein,including published or corresponding U.S. or foreign patentapplications, issued U.S. or foreign patents, and any other references,are each incorporated by reference in their entireties, including alldata, tables, figures, and text presented in the cited references.

Terms that are derivative from one another may be used interchangeably,except where context mandates otherwise. For example, amine and amino;carboxy, carboxyl and carboxylic; acrylic and acrylate; hydroxyl andhydroxyl; hydrogen, hydride and proton; epoxy and epoxide; etc.

Insulating Foams Generally

The terms “foamable composition” and “foam composition” may beinterchangeably used in this application. In addition, the terms“oligomer” and “prepolymer” may be interchangeably used herein.

The term “R-value” is the commercial unit used to measure theeffectiveness of thermal insulation and is the reciprocal of its thermalconductance which, for “slab” materials having substantially parallelfaces, is defined as the rate of flow of thermal energy (BTU/hr or Watt)per unit area (square foot=ft² or square meter=m²) per degree oftemperature difference (Fahrenheit or Kelvin) across the thickness ofthe slab material (inches or meters). Inconsistencies in the literaturesometimes confuse the intrinsic thermal properties resistivity, r, (andconductivity, k), with the total material properties resistance, R, (andconductance, C), the difference being that the intrinsic properties aredefined as being per unit thickness, whereas resistance and conductance(often modified by “total”) are dependent on the thickness of thematerial, which may or may not be 1 unit. This confusion, compounded bymultiple measurement systems, produces an array of complex and confusingunits the most common of which are:

English Metric/SI (inch-pound) units Intrinsic resistivity, r hr*ft²*°F. ° K*m (conductivity, k, is reciprocal) BTU*in W Total materialresistance, R hr*ft²*° F. ° K*m² (conductance, C, is reciprocal) BTU WFor ease of comparison of materials of differing thicknesses, thebuilding industry sometimes reports thermal resistance (or conductance)per unit thickness (e.g. per inch) effectively converting it to thermalresistivity (conductivity), but retains the traditional symbol, R orR-value.

“Sealing” as used herein refers to the prevention or hindering of themovement of air such as drafts (i.e. convection) that can move throughcavities, gaps, and poorly sealed seams, whereas “insulating” refers tothe prevention or hindering of all forms of heat transfer, includingconvection, conduction and radiation. Thus, sealing is a specializedcase of insulating. Sealing is also important for noise reduction.

In some embodiments, the present invention relates to two-part foamablecompositions. The foams may be used to fill cavities of buildings toimprove the sealing and insulation properties. Additionally, theinventive foams may be used to seal cracks and crevices, such as thosearound windows and doors. In alternative uses, the inventive foams canbe used in spray, molding, extrusion, and injection molding (e.g.,reaction injection molding (RIM)) applications. In one exemplaryembodiment, the inventive foam is formed from two components or reactionmixtures, namely, an A-side and a B-side. The A side may contain anacrylic or epoxy resin, or both, along with other additives such assurfactants and rheology modifiers. The B side contains a urethanereactant with reactive functional groups—such as acrylic, carboxy, amineor hydroxy—and no free isocyanate groups. The B-side may optionallycontain additives such as a surfactant and/or rheology modifier. One orboth of the A side and B side contains a blowing agent.

Urethane Reactants

A wide variety of urethane reactants are useful with the invention. Insome embodiments the urethane reactant is a preformed urethane adduct,while in other embodiments the urethane reactant is two or more buildingblocks that from the urethane adduct in situ. Urethane reactants haveurethane bond backbones with reactive functional groups other thanisocyanates found at the termini and/or pendent from side chains. Theymay be categorized into two broad groups based on the method used tomanufacture them. When isocyanate monomers are used to form the urethaneor polyurethane adducts, the oligomer or prepolymer may be referred toas an “isocyanate-based adduct” or “IBA”, and in this case theisocyanate ends are blocked or capped with other suitable reactivefunctional groups. This first type is generally used in the invention aspreformed adduct to avoid exposure to isocyanate monomers. Whennon-isocyanate monomers are used, the oligomer or prepolymer may bereferred to as a “non-isocyanate-based adduct” or “NIBA”—which issometime also referred to as a non-isocyanate polyurethane or “NIPU”.The chemistries used to make NIBAs or NIPUs avoids the isocyanate endsdirectly and instead introduces amine and/or carboxyl functional groups.This second type may be used as preformed adduct or as the individualreactive building blocks of the urethane reactant.

The urethane reactants may be present in an amount from about 5 to about90 percent by weight of the foamable composition, and in exemplaryembodiments, in an amount from about 25 to about 90 percent by weight,or from about 25 to about 40 percent by weight.

Preformed Urethane Oligomers

Polyurethanes are traditionally made using a di or polyisocyanatemonomer of the general formula O═C═N—R¹—N═C═O and a di or polyol monomerof general formula HO—R²—OH, where R¹ and R² are various backbones, thenature of which helps classify and define the precise properties of thepolymer. For example, the R-groups may be aliphatic, aromatic,polyester, polyether, polybutadiene, or mixed; and they may be linear,simple branched or dendritic in nature. The two monomers react to formurethane oligomers or prepolymers of the general formula I:

O═C═N—R¹—[NC(O)O—R²—OC(O)—N—R¹—]_(k)—N═C═O  (I)

wherein k is an integer from 2 to about 50 or more depending on thepolymerization conditions, the relative amounts of each monomer and theuse of chain terminators—all of which is well known in the art. FormulaI assumes a linear oligomer, but synthesis of branched oligomers ispossible from substituents on either R¹ or R². Substituents on either R¹or R² can also impart other functional groups, such as carboxyl, amino,hydroxyl, that can be used to enhance the crosslinking reactions. Themost common isocyanate monomers for use in making polyurethanes are:diphenylmethane 4,4-diisocyanate (“MDI”), naphthalene 1,5-diisocyanate(“NDI”), toluene diisocyanate (“TDI”) and hexamethylene diisocyanate(“HDI”). Other aliphatic polyisocyanate examples include isophoronediisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,4-tetramethylenediisocyanate, 1,5-pentamethylene diisocyanate, 1,7-heptamethylenediisocyanate, 1,8-octamethylene diisocyanate, 1,9-nonamethylenediisocyanate, 1,10-decamethylene diisocyanate,2,2,4-trimethyl-1,5-pentamethylene diisocyanate,2,2′-dimethyl-1,5-pentamethylene diisocyanate,3-methoxy-1,6-hexamethylene diisocyanate, 3-butoxy-1,6-hexamethylene,omega, omega'-dipropylether diisocyanate, 1,4-cyclohexyl diisocyanate,1,3-cyclohexyl diisocyanate, trimethylhexylmethylene diisocyanate andcombinations thereof.

A wide variety of polyether, polyester, polycarbonate, hydrocarbon,aromatic and other polyols may be used. For example, representativepolyether polyols useful in preparing the urethane oligomers includestraight or branched alkylene oxides having from one to twelve carbonatoms (C1-12), prepared by methods known in the art. Desirably, thepolyether polyols have an average molecular weight, as determined byvapor pressure osmometry (ASTM-D 3592), sufficient to give the urethaneoligomer a molecular weight of about 6,000 daltons, desirably not morethan 5,000 daltons and more desirably not more than 4,000 daltons.Examples include, without limitation, polytetramethylene polyol,polymethylene oxide polyol, polyethylene oxide polyol, polypropyleneoxide polyol, polybutylene oxide polyol, tetrahydrofuran(THF)-sym-polyether polyol and combinations thereof.

Representative hydrocarbon polyols used to prepare the urethaneoligomers also include hydrocarbon polyols, straight or branched, havinga molecular weight of from about 600 to 4,000. Non-limiting examplesinclude fully or partially hydrogenated polybutadiene polyol,polybutadiene polyol hydrogenated to an iodine number of from 9 to 21,and fully or partially hydrogenated polyisobutylene polyol.

Representative polycarbonate polyols used to prepare the urethaneoligomers include but are not limited to the reaction products ofdialkyl carbonate with an alkylene diol, optionally copolymerized withalkylene ether diols.

Notably, Formula I still contains isocyanate termini and thus is not aurethane reactant as defined herein. The isocyanate groups are highlyreactive and may easily be replaced or capped with known chemistries.For example, urethane acrylate oligomers (UAOs) are known to thoseskilled in the art of coatings. Many are available from suppliers likeSartomer (Exton, Pa.) and Bomar Specialties (Torrington, Conn.). TheUAOs may be made via isocyanate or non-isocyanate chemistries, providedthe ends can be capped acrylates or methacrylates.

More specifically, useful di- or polyfunctionalized urethane acrylatesinclude aliphatic polyester urethane diacrylates. Aliphatic polyesterurethane diacrylates having high molecular weights, such as 2,000 to7,000, are particularly desirable. Other mono-, di-, or polyfunctionalurethane acrylate oligomers useful in the present invention can bedescribed as the acrylated reaction product of an aliphatic alcohol,such as polycarbonate polyol, a polyether polyol, or ethylene glycolmonoacrylate, and a polyisocyanate.

As noted above, the nature of R¹ and R² can create many differenturethane oligomers and prepolymers having different properties. Thealiphatic and aromatic R groups may perform differently; the straightand branched R groups are likely to perform differently; and the ratiobetween the polyester and polyether nature of the R groups are likely toperform differently. The distance between functional groups and therotational degrees of freedom of the backbones likely impact propertiessuch as the setting time or speed of reaction, viscosity, solubility andother properties of the oligomer. In some embodiments, the oligomerfunctionality is greater than 2, such as 3, 4 or 6. Exemplary UAOsinclude Bomar BR series (100, 300, 400, 500, 700 and 900) and Sartomerseries CN 97x, 99x, 90xx, and 91xx.

Other potential reactive end caps are useful besides acrylates. Forexample, siloxy and carboxyl ends have been described in co-pending U.S.patent application Ser. No. 13/221,373. Additionally, reactive aminefunctional end caps may be obtained by reacting the isocyanate ends withprimary or secondary amines, or by adducts preformed using buildingblocks described below.

Urethane Reactant Building Blocks

Amine functional ends may also obtained by another known route, usingcyclocarbonate and polyamine chemistry as taught in U.S. Pat. No.5,175,231 to Rappoport, et al. This chemistry has been used to makenon-isocyanate polyurethane (NIPU) foams, but is notoriously slow. Thus,although foams made directly from NIPU chemistry have generally beenslow to cure, the building blocks may be used in the invention in aprocess accelerated with heat or, alternatively, amine-capped urethaneoligomer adducts can be preformed. The presence of a di- or poly epoxyresin in the other side, with or without acrylate monomer, forms ahybrid non-isocyanate polyurethane (HNIPU).

The cyclocarbonates may be prepared as described in U.S. Pat. No.5,175,231 to Rappoport, et al.; or from bio-based epoxies, such asepoxidized soy bean oil (EBSO), thereby resulting in a bio-basednon-isocyanate polyurethane (NIPU) or a bio-based hybrid non-isocyanatepolyurethane (HNIPU). Such cyclocarbonates may be used in the A-side.Hybrid non-isocyanate polyurethane may also be formed when an epoxyfunctional group is present in the other side. It is to be appreciatedthat the epoxy resin may also be a bio-based epoxy (e.g., epoxidized soybean oil (ESBO) or a partially bio-based epoxy.

The A-side also contains a polyfunctional amine, preferably having twoor more primary amines. Examples of suitable polyfunctional aminesinclude isophorone diamines, trimethylhexamethylene diamines,polyoxyalkyleneamines (e.g., Jeffamines®, commercially available fromHuntsman), and aliphatic amines (e.g., Ancamines®, commerciallyavailable from Air Products), Epikure™ line commercially available fromMomentive, (Columbus, Ohio). In at least one exemplary embodiment, thedi- or polyamine crosslinking agent is one or more of an amidoamine, acyclic, aliphatic, or aromatic di- or polyamine containing primaryand/or secondary amine functionalities or mixtures thereof. Thepolyfunctional amine crosslinking agent may be present in the A-side inan amount from about 3.0 to about 30% by weight of the dry foamcomposition, or in an amount from about 1.0 to about 20% by weight.Although a 1:1 mole ratio of the functional groups is preferred, thismolar ratio is variable and may encompass a wider range, such as, forexample, from 0.5:1 to 2:1 to provide the optimum crosslinking in thefinal foam products.

The B-side of the foam composition, as indicated previously, contains adi- or poly epoxy resin and preferably an acrylate monomer. The acrylatemonomer and polyamine may react rapidly to produce internal heat toaccelerate formation of the urethane reactant from the cyclocarbonateand polyamine building blocks. Optionally a plasticizer and/or asurfactant and/or a non-reactive resin may be included. The non-reactiveresin is a resin that does not react with the di- or polyaminecrosslinking agent, but is otherwise non-limiting.

Crosslinker

The crosslinker contains reactive functional groups that react with theurethane reactant and optional resin polymer. The nature of the reactivefunctional group will depend on the nature of the other functionalgroups. For example, for urethane acrylate oligomers, a di- or polyaminecrosslinker is used, and those polyamines described above may be used ascrosslinker. For amine-functional urethane reactants, an epoxy oracrylic functional crosslinker may used and this crosslinker may besupplied as the resin polymer, in which case additional or differentresin polymer may still be optionally added. Resin polymers aredescribed below.

It will be understood that function of the urethane reactant the choiceof agents (urethane reactant, crosslinker and optional resin polymer) tomix together in either the A-side or B-side will depend on thereactivity of their respective functional groups. In general, aminefunctionalities must be kept separate from epoxide and acrylate moieties(whether present in the resin or urethane reactant), but polyamines maybe combined with amine-functionalized urethane reactants (e.g. NIPU),while epoxy and/or acrylic resins are employed in the other part.

The crosslinking agent may be present in an amount from about 3.0 toabout 30% by weight of the dry foam composition, or in an amount fromabout 1.0 to about 20% by weight. Although a 1:1 mole ratio of thefunctional groups is preferred, this molar ratio is variable and mayencompass a wider range, such as, for example, from 0.5:1 to 2:1 toprovide the optimum crosslinking in the final foam products.

Resin Polymers

Resin polymers have functional groups that react with and crosslink withthe functional moieties of the urethane reactants. Epoxy resins arewidely known and used in the polymer arts. Epoxy resins are typicallycharacterized by molecular weight and by a measure of the number ofavailable epoxy moieties. Such measures may include “epoxide number” or“epoxide equivalents” or “weight per epoxide”. Useful epoxy resins haveepoxide equivalents from about 150 to about 400, or from about 180 toabout 325. Illustrative, but non-limiting epoxy resins are availablefrom Dow, Hexion and Momentive under the tradenames: DER 331 (epoxideequivalent weight in g/eq=182-192); Epon 828 (wt/epoxide=185-192); Epon8111 (wt/epoxide=300-320), for example. The epoxy resin may be presentin the formulation in amounts from about 5 to about 70 weight percent,more typically from about 15 to about 60 weight percent.

In addition to the epoxy resin and urethane reactant that mainly formthe polymer film of the cells of the foam, it is generally desirable andimportant to include acrylate monomers, especially when the urethanereactant is not a preformed adduct. The acrylate monomers function ascure accelerators and modifiers for the epoxy/amine polymerizationcuring reaction. Suitable acrylate monomers include aliphatic acrylatemonomers such as, for example, MCure 400, MCure 400Ep, MCure 202, SR399, SR 610, SR 492, SR 259, SR 248, SR 247, SR 214, and CD 9021 (allcommercially available from Sartomer, Exton, Pa.). Acrylate monomers maybe present in the formulation in amounts from about 10 to about 60weight percent, more typically from about 25 to about 40 weight percent.

Blowing Agent

In addition to the components set forth above, at least one side,A-side, B-side or both, contains a blowing agent. Hydrocarbon andhalogenated/fluorinated hydrocarbon blowing agents are well known. Forexample halogenated aliphatic hydrocarbon blowing agents include“Freon-like” fluorocarbons, chlorocarbons and chlorofluorocarbons.Examples of partially or fully halogenated fluorocarbons include methylfluoride, difluoromethane (HFC-32), perfluoromethane, ethyl fluoride(HFC-161), 1,2-difluoroethane (HFC-142), 1,1-difluoroethane (HFC-152a),1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoro-ethane (HFC-134a),1,1,2,2-tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125),perfluoroethane, 2,2-difluoropropane (HFC-272fb), 1,1,1-trifluoropropane(HFC-263fb), 1,1,1,3,3-pentafluoropropane (HFC 245fa),1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), perfluoropropane,1,1,1,3,3-pentafluorobutane (HFC-365mfc), perfluorobutane, andperfluorocyclobutane. Examples of partially halogenated chlorocarbonsand mixed, chlorofluorocarbons for use in this invention include methylchloride, methylene chloride, chlorodifluoromethane (HCFC-22), ethylchloride, 1,1,1-trichloroethane, 1,1,1-trifluoroethane,1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane(HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124), pentafluoroethane,dichloropropane, and the like. Examples of fully halogenatedchlorofluorocarbons include trichloromonofluoromethane (CFC-11),dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113),dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane,dichlorohexafluoropropane, and HFC-245fa

Desirably, the blowing agent is non-reactive (with other components) andenvironmentally friendly and has zero or very little ozone depletionpotential (ODP) and little to no global warming potential (GWP). Theblowing agent may be a chemical compound that, when heat or lightactivated, forms a gas. The generated gas may be N₂, O₂, H₂, or othernon-carcinogenic, gases. For instance, azodicarbonamide is a chemicalcompound that, upon heating, releases N2 gas, and would be a suitableblowing agent in the foamable composition. Additionally, alkylsiloxanes,such as XIAMETER®, and MHX-1107 Fluid (all available from Dow Corning(Midland, Mich.)), which may release H₂ when reacting with aminehardeners, may be used as a blowing agent and/or as a crosslinking agentin the instant invention. Other examples include diazo compounds (i.e.,CH₂N₂) and aliphatic azide (i.e., R—N═N=N), which decompose onirradiation to give nitrogen gas.

Phase change blowing agents such as low boiling point hydrocarbons(e.g., cyclopentane and n-pentane) and inert gases such as air andnitrogen can also be used. It is to be appreciated that the chemicalcompound is not a conventional blowing agent in the sense that it is ahydro-fluorocarbon (HFC) or a hydro-chloro-fluorocarbon (HCFC) blowingagent, such as, for example, HFC-245fa. Another blowing agent, FEA-1100(1,1,1,4,4,4-hexafluoro-2-butene), is a fourth generation fluorocarbonproduct available from DuPont. According to properties described in awhite paper authored by Loh, et al, and published at:http://www2.dupont.com/Formacel/en_US/assets/downloads/white_paper_FEA-1100.pdf(as of Jul. 21, 2011) FEA-1100 has shown very low global warmingpotential, zero ozone depletion potential, is non-flammable and stableat ambient room temperatures, and has higher boiling point than HFC245fa, making it safer and easier to work with. Additionally, theblowing agent may be formed of more than one blowing agent (e.g.,blowing agent package), such as, for example, the combination of achemical blowing agent and a gas (e.g. HFC blowing agent), or blends oftwo HFC blowing agents. The blowing agent may be present in an amountfrom about 7 to about 40 percent by weight of the composition, and inexemplary embodiments, in an amount from about 15 to about 30 percent byweight.

The A-side and the B-side may be added at a 1:1, 1:2, 1:3 or 1:4 ratio(A-side:B-side), and in exemplary embodiments, they are added in anamount in a 1:2 ratio. In addition, polymer microspheres such as, butnot limited to, Expancel® 031 DUX 40 could be used to help in foaming,to increase the viscosity of the A-side and/or the B-side, and to reducethe density of the foam. Because microspheres have a solid form, theynaturally increase the viscosity of the side in which it is added. Inaddition, the microspheres expand at a certain temperature, therebyresulting in a closed-cell sphere that contains a blowing agent. Thisblowing agent within the microsphere may act as a blowing agent in thefoamable composition.

Rheology Modifiers

Controlling the rate of polymerization and the rate of blowing agent isimportant to the forming of good quality foams, particularly foams thatdepend on a vertical substrate for support. It is also desirable thatthe A-side and the B-side have the same or nearly the same viscosity toachieve proper mixing of the A-side components with the B-sidecomponents. A 1:1 ratio promotes easy mixing of the components of theA-side and B-side. Additionally, it is desirable for the A-side andB-side reactants to have low enough initial viscosity that they can besprayed from a spray device, such as an application gun. For thisreason, an optional but desirable component of the foaming compositionis a rheology modifier—also known as a thixotrope—that can affect theflow properties of a liquid. A thixotropic mixture has high viscosityand resistance to flow at low shear (e.g. once sprayed into a cavity oronto a vertical surface) and lower viscosity when sheared (e.g. whenshaken; stirred or sprayed from the application device). In foamcompositions of the invention, rheology modifiers allow for lowviscosity under the shear for the application device but, once sprayed,they help keep the reactants in place on a substrate against the forceof gravity until the foaming and polymerization reactions are completeor at least sufficiently progressed. The rheology modifier may bepresent in an amount up to about 50% by weight of the dry foamcomposition. Preferably, the amount of rheology modifier present isabout 0.1% to about 20% by weight, based on the dry foamablecomposition, depending upon the nature of the modifier. Rheologymodifiers may be divided into five different major groups: cellulosicderivatives, polyamides, carboxyl-containing acrylics, associativethickeners, and inorganics like clay and silica. See. e.g. Werner Blankpresentation at: http://www.wernerblank.com/pdfiles/rheology.pdf.

Cellulosic derivatives may operate by any of several mechanisms,including contribution to hydrodynamic volume, chain entanglement, andflocculation depletion. Suitable agents for use in the foamablecomposition include methyl cellulose, ethyl cellulose, hydroxyethylcellulose (e.g., Cellosize™ available from Union Carbide). Usefulcarboxyl-acrylates include alkaline swellable polyacrylates (e.g.,Paragum 500 available from Para-Chem), sodium polyacrylates (e.g.,Paragum 104 available from Para-Chem).

Associative thickeners may affect the rheology by adsorption (e.g.hydrophobic or ion-dipole), inter- or intra-molecular self association,or micelle formation. Useful associative thickeners include thoseclassed as hydrophobically-modified ethoxylated urethanes (HEUR-type)including those sold under the tradenames Acrysol™ (RM, TT and QR typesat least Dow Chemical, Midland, Mich.), and KStay 700 (King Industries,Norwalk, Conn.); as hydrophobically-modified alkalai-swellable emulsions(HASE-type); a hybrid known as HEURASE-type; andhydrophobically-modified hydroxyethyl cellulose, (HMHEC-type).

Many rheology modifiers are inorganic minerals, clays or modified clays.Clay is common name for a wide variety of weathered mineral or igneousrock, largely feldspar. Various classification schemes, such as theNickel-Strunz classification, divide up mineral clays according tocomposition and/or structure. Suitable rheology modifiers may be foundin the kaolinite group, the smectite or montmorillonite group and theillite group. Generally, these groups contain sheets or layers formed ofspecific tetrahedral and/or octahedral structures of aluminum andsilicon oxides. The layers or platelets are held together by ionic bondswith charged ions (usually cations) located between the layers. TheNickel-Strunz classification (version 10) divides silicates (group 9)into nine different subcategories, the most useful being phyllosilicates(group 9E), which itself is divided into nine subcategories, the twomost useful being 9EC (with mica sheets) and 9ED (with kaolin layers).Exemplary clays from these groups include kaolin, montmorillonite orsmectite, talc, mondorite, nontronite, muscovite, vermiculite, saponite,hectorite, rectorite, and minnesotaite. Bentonite is a useful impureclay largely containing montmorillonite.

It is the layers or “platelets” of phyllosilicates that give them manyof their properties, including the plasticity for use as pottery. Whenthe layers are of thickness dimensions in the few nanometer range, theyare often referred to as nanoclays. An example is the NANOLIN DK seriesof nanoclays available from Zhejiang Fenghong Clay Chemicals Co., LTD.,which are made from highly purified smectite that exhibits ultra-finephase dimensions. The size of these nanoclays is typically in the rangeof 1-100 nm while been fully dispersed, the average fully dispersedthickness of platelet is around 25 nm; the aspect ratio is 100-1000.

Modified clays are formed when various processes are used to separateand expand the layers or platelets. Intercalation, exfoliation andfuming are processes that modify the layered structure. Intercalationinserts a polymer or other molecule between the platelet layers toisolate them, but without much physical separation. Exfoliation, on theother hand inserts a polymer or molecule and expands the space betweenlayers by 10-20 fold. Fuming is a flaming process that introduceshydroxyl groups onto the surface of the silica structures.

Most clays are inorganic and therefore not very compatible with polymerfoams. A specific type of modified clay that impacts hydrophilicity andsolubility produces polymer-compatible clays known as “organoclays.”Organoclays are modified by the replacement of the cation (usuallysodium) between layers with alkylammonium (R₄N⁺) compounds, a type ofsurfactant. The nitrogen end of the quaternary amine, the hydrophilicend, is positively charged, and ion exchanges onto the clay platelet forsodium or calcium. The amines used generally have long chain R groupswith 12-18 carbon atoms, making them more compatible with many organicpolymers. After about 30 percent of the clay surface is coated withthese amines it becomes hydrophobic and, with certain amines,organophilic. Additionally, exfoliation of organoclays becomes easiersince there is a larger distance between the platelets due to the biggersize of the ammonium salts compared to sodium ions.

Some non-limiting examples of the many clay-based rheology modifiersinclude Laponite and Garamite 1958 (Southern Clay Products), and thehigh temperature resistant Rilenite HT extra. Some non-limiting examplesof the many rheology modifiers based on fumed alumina or fumed silica,include Aerosil and Cab-O-Sil® TS-720 (Cabot Corp.)

As described above, it is desirable that the A-side and the B-side havethe same or nearly the same viscosity to permit easy application andmixing of the components of the A-side and B-side. The thickening agentsmay be present in the A-side and the B-side, respectively, in an amountup to about 50% by weight of the dry foam composition. The thickeningagent in the A-side may be the same or different from one in the B-side,if also present there. In at least one exemplary embodiment, the amountof thickening agent present in the A-side is from about 0.1 to about10.0% by weight, based on the dry foamable composition, and the amountof thickening agent present in the B-side is from about 0.1 to about10.0% by weight, based on the dry foamable composition, depending uponthe nature of the thickening agent.

Rheology modifiers or thickeners should be selected carefully so as notto interfere with desired final foam properties (such as percentageclosed cell content and density) while they provide the needed viscosityto assist in sag prevention. For example it was shown that CabosilTS-720, at a concentration effective for sag prevention, produced foamsof lower closed cell content. On the other hand, the modified nanoclay,Garamite 1958, at a concentration effective for sag prevention, producedfoams of higher closed cell content. This particular rheology modifier(Garamite 1958) was found useful in a wide variety of foam chemistries,and is expected to improve bio-based polyurethane foams as well.Bio-based polyurethane spray foams are generally slower to react thanthe petroleum based polyurethane foams, likely due to the higherproportion of secondary and tertiary polyols. So the use of a rheologymodifier, such as Garamite, can greatly help bio-based polyurethanemarket.

Other Optional Additives

In the spray foam of the present invention, the A- or B-side may alsoinclude other optional, additional components such as, for example, foampromoters, opacifiers, accelerators, foam stabilizers, dyes (e.g., diazoor benzimidazolone family of organic dyes), color indicators, gellingagents, flame retardants, biocides, fungicides, algaecides, fillers,and/or conventional blowing agents. It is to be appreciated that amaterial will often serve more than one of the aforementioned functions,as may be evident to one skilled in the art, even though the materialmay be primarily discussed only under one functional heading herein. Theadditives are desirably chosen and used in a way such that the additivesdo not interfere with the mixing of the ingredients, the cure of thereactive mixture, the foaming of the composition, or the finalproperties of the foam.

The A- and/or B-side may optionally contain a plasticizer. Theplasticizer for use in the A-side and B-side is not particularlylimiting, and includes plasticizers such as phthalate ester, dimethyladipate, dimethyl phthalate, epoxidized crop oils (e.g., Drapex 10.4,Drapex 4.4, and Drapex 6.8 available from Chemtura, butyl benzoate,Benzoflex® 2088 (a benzoate ester plasticizer available from GenoviqueSpecialties), Benzoflex® LA-705 (a benzoate ester plasticizer availablefrom Genovique Specialties), Triton® X-100 (anoctylphenoxypolyethoxyethanol available from Cognis), PEG-400 (apolyethylene glycol available from Cognis), Cifroflex® 2 (a triethylcitrate available from Vertellus® Specialties), bio-based oils, andCitroflex® 4 (a tributyl citrate available from Vertellus® Specialties).The plasticizer may be present in an amount from about 0 to about 15% byweight.

Additionally, the presence of the plasticizer permits for the inclusionof other solid materials that may add functionality and/or cost savingsto the final foamed product. For instance, fillers (e.g., calciumcarbonate and wollastonite fibers), nucleating agents (e.g., talc),and/or foaming agents (e.g., sodium bicarbonate) can be included in theB-side of the foamable composition.

Also, the A-side and/or the B-side may contain one or more surfactantsto lower surface tension, to assist in mixing incompatible formulationingredients, to promote and stabilize the nucleation of bubbles duringmixing, to stabilize the early stages of the reacting foam structureuntil sufficient polymerization has occurred to form a self-supportingnetwork, and to counteract the defoaming effect of any solids added toor formed during the foam reaction. Useful surfactants include, but arenot limited to, silicone surfactants, siloxane-polyoxyalkylene blockcopolymers such as Niax Silicone L-6900 (available commercially from GESilicones (Friendly, West Va.); Dabco DC-5598 (a silicone surfactantcommercially available from Air Products and Chemicals, Inc. (Allentown,Pa.); Tegostab B 8512 (a silicone surfactant commercially available fromGoldschmidt Chemical Corp. (Essen, Germany)); Vorasurf 504 (anon-silicone surfactant commercially available from Dow Chemical Co.(Midland, Mich.)); Triton™ GR-5M (a sulfosuccinate anionic surfactantcommercially available from Dow Chemical Co. (Midland, Mich.)); andDabco® DC-193 (a silicone based co-polymer surfactant available from AirProducts and Chemicals, Inc. (Allentown, Pa.)). The surfactant may bepresent in the A- and/or B-side in an amount from about 0 to about 10.0%by weight of the dry foam composition.

In the spray foam of the present invention, the A- or B-side may alsoinclude other optional, additional components such as, for example, foampromoters, opacifiers, accelerators, foam stabilizers, dyes (e.g., diazoor benzimidazolone family of organic dyes), color indicators, gellingagents, flame retardants, biocides, fungicides, algaecides, fillers,and/or conventional blowing agents. It is to be appreciated that amaterial will often serve more than one of the aforementioned functions,as may be evident to one skilled in the art, even though the materialmay be primarily discussed only under one functional heading herein. Theadditives are desirably chosen and used in a way such that the additivesdo not interfere with the mixing of the ingredients, the cure of thereactive mixture, the foaming of the composition, or the finalproperties of the foam.

The A- and/or B-side may also include other optional, additionalcomponents such as, for example, foam promoters, opacifiers,accelerators, foam stabilizers, dyes (e.g., diazo or benzimidazolonefamily of organic dyes), color indicators, gelling agents, flameretardants, biocides, fungicides, algaecides, corrosion inhibitors,fillers, and/or conventional blowing agents. It is to be appreciatedthat a material will often serve more than one of the aforementionedfunctions, as may be evident to one skilled in the art, even though thematerial may be primarily discussed only under one functional headingherein. The additives are desirably chosen and used in a way such thatthe additives do not interfere with the mixing of the ingredients, thecure of the reactive mixture, the foaming of the composition, or thefinal properties of the foam.

Methods of Use

To form a two-part spray foam of the present invention, the componentsof the A-side and the components of the B-side are delivered throughseparate lines into a spray device, such as an impingement-type spraygun. The two components are pumped through small orifices at highpressure to form streams of the individual components of the A-side andthe B-side. The streams of the first and second components intersect andmix with each other within the gun and begin to react. Depending on thecomponents of the blowing agent package in the A-side and the B-side,the gas generated may be N₂, O₂, H₂, or other non-carcinogenic gases.The foaming reaction occurs until all of the blowing agent(s) have beenreacted and no more gas is generated.

In at least one exemplary embodiment, the A- and/or B-side is heated toa desired temperature (e.g., about 120° F. to about 150° F. (or higher))prior to adding the blowing agent. In such an embodiment, the blowingagent is added through a separate line to the heated mixture. In anotherexemplary embodiment, the A-side and the B-side, at least one of whichcontains a blowing agent, are separately heated to a desired temperatureprior to mixing the two sides together. The A-side and the B-side may beheated to the same temperature or to different temperatures. Forexample, the side containing the blowing agent may be heated to atemperature lower than the side that does not contain the blowing agentto reduce the risk of evaporating or skipping the blowing agent.Alternatively, the A-side and the B-side, at least one of which containsa blowing agent, may first be mixed together and then heated to adesired temperature (e.g., about 120° F. to about 150° F. (or higher)).The reaction mixture (whether the A- and B-side are separately heated orwhether the A- and B-side are mixed and then heated) may optionally bekept at the desired temperature until the exotherm of the reaction ishigher than the desired temperature. By heating the A- and B-side (oneside containing the blowing agent), the reaction proceeds more quicklyand results in a decreased tack-free time.

In a further exemplary embodiment, the A- and B-side are heated prior tomixing the two sides together. The heat may be supplied as externallyapplied heat (as discussed above) or internally generated heat from achemical reaction. As one example of chemically generated heat, Epon™8111 (a multifunctional resin containing both epoxide groups andreactive unsaturation (commercially available from Cognis)) and sodiumhydroxide may be added to the A-side and Epikure™ 3271 (a modifiedaliphatic amine (commercially available from Hexion/Momentive)) may beadded to the B-side. The reaction between the epoxy in the Epon™ 8111and the aliphatic amine in the Epikure™ 3271 in the presence of sodiumhydroxide is very fast and generates a significant amount of heat as thereaction takes place. It has been discovered that the addition of Epon™8111 and Epikure™ 3271 to the A- and B-side, respectively, results in afoam that raises rapidly and becomes tack-free or essentially tack-freean about 2 minutes or less. Also addition of acrylate monomers such asthe MCure or SR products previously mentioned to the epoxy side andaddition of Epikure3271 in side B can reduce the tack free time to lessthan 1 minute.

As used herein “tack-free” is a preliminary measure of cure state and aproxy measure for the resistance to sag that is desired of foams used inthe building industry. As the polymer film forms and expands under theeffect of the blowing agent, a skin forms on the outer surface. Whenthis skin can be touched without any foam composition residue remainingon the finger it is said to be “tack-free.” In general, the formation ofsuch a tack-free skin within these times is consistent with the abilityof a foam to resist the force of gravity long enough for the polymerstructure to form and set to avoid running or sagging in the wallcavity. A further measure of the cure state is referred to as“resilient” or “cured throughout.” This is a more fully cured state thatallows a finger to depress the foam, and the foam will rebound back toessentially its original state. Spray foams of the invention generallyare tack-free within 4 minutes, more typically within 2 minutes or oneminute; and are resilient within about 20 minutes, more typically withinabout 15 or 10 minutes.

Although not wishing to be bound by theory, it is believed that anadvantage of utilizing chemically generated heat (e.g., over externallyapplied heat) is that the reaction between the acrylate monomer moieties(e.g. MCure 400) and polyamine curing agents (e.g. Epikure™ 3271)provides the required heat for both the NIPU and HNIPU reactions. Forexample, it is believed that two reactions are sequentially takingplace. These reactions are as follows:

-   -   1. acrylate monomer (such as Mcure 400 or SR399)+polyamine (such        as Epikure™ 3271) 4 heat and primary network structure    -   2. epoxy resin+NIPU+heat→more network structure and        polymerization

In reaction number “1”, the reaction between acrylic functionalities andEpikure™ 3271, the amine functional group of the Epikure™ 3271 is addedto the acrylic functional group by a Michael addition. This reaction isa fast, exothermic reaction which provides the primary network for thefoam and which also generates the required heat for the reaction betweenthe cyclocarbonate/amine and the epoxy/amine. Other compounds containingacrylic functional groups such as, but not limited to, SR 399, MCure400, MCure 400Ep, MCure 202, SR 610, SR 492, SR 259, SR 248, SR 247, SR214, and CD 9021 (all commercially available from Sartomer) can be usedin place of Epon™ 8111. Additionally, amines such astriethylenetetramine (TETA), Ancamines® (Huntsman), and Jeffamines®(Huntsman) can be used in place of Epikure™ 3271.

Additionally, it is to be appreciated that the crosslinking is importantfor capturing the bubbles generated by the evolution of the gas in theiroriginal, fine structure before they can coalesce and escape the foam. Afine foam structure is more desirable and more beneficial than a coarsefoam structure in order to achieve high thermal performance. Also, thecrosslinking of the cyclocarbonates and/or the di- or poly epoxy resinwith the amine builds strength in the foam and permits the foam towithstand the force of gravity when it is placed, for example, in avertical wall cavity during application. The resulting resistance toheat transfer, or R-value, may be as from about 3.0 to about 7.0 perinch. It is also to be appreciated that the foam formed may have an openor closed cell structure and that the oligomer and ratio ofcyclocarbonate functional groups to epoxy functional groups can bemodified to result in a rigid or a flexible polyurethane foam and/or anopen or closed foam.

In one exemplary embodiment of the invention, a phase change blowingagent is utilized as the blowing agent. To form a foam utilizing a phasechange blowing agent such as a low boiling point hydrocarbon or inertgas, a compound (e.g., a monomer or an oligomer) having thereon at leastone cyclocarbonate group and optionally a di- or poly epoxy resin, a di-or polyfunctional amine crosslinking agent, and phase change blowingagent are pressurized, such as in a pressurized spray-type container.Upon mixing the two sides, the amine cross linking agent reacts with thecyclocarbonate functionalities and/or the epoxy resin to form thepolymer backbone, the blowing agent is released from the pressurizedcontainer (e.g., released into atmospheric pressure or depressurized),and the blowing agent changes from a liquid to a gas to initiate thefoaming reaction to foam the polymer backbone. The foaming reactioncontinues until all of the blowing agent has been converted into a gasand all the amine groups have been reacted.

In yet another embodiment, a method of forming a non-isocyanate foam isprovided that includes (1) delivering a first component that includes atleast one urethane amine oligomer made by reacting a cyclocarbonate anda di- or -polyamine crosslinking agent as described above (i.e., made bya non-isocyanate reaction) through a first delivery line to anapplication device, (2) delivering a second component that includes adi- or poly epoxy resin to the application device, where one of thefirst and second component further includes a blowing agent, (3) mixingthe first and second components within the application device to form areaction mixture, and (4) permitting the amine and epoxy to chemicallyreact while the blowing agent forms a gas to initiate a foaming reactionand form a foam. The first component may further include a firstplasticizer and/or a surfactant and the second component may furtherinclude a second plasticizer and/or a non-reactive resin. In exemplaryembodiments, a compound (e.g., a monomer or an oligomer) having thereonat least one cyclocarbonate group and an amine are pre-reacted togenerate the urethane oligomer, which is then reacted with the di- orpoly epoxy.

In use, the inventive foams may be sprayed into or onto a building'sstructural components. As used herein, “Structural components” of abuilding or building structure include, but are not limited to, wallstuds, including king studs and cripple studs, sheathing, includingfoams, OSB, particleboard, plywood, Celotex™, Tyvek™ and the like, floorjoists, bandjoists, subflooring, sole plates and top plates, headers,beams, rafters, trusses, windowframes, doorframes and the like—and toany cavity between any such structural component. Thus, foams may besprayed into an open cavity, such as between wall studs, or into aclosed cavity where it expands to seal any open spaces. The applicationis desirably a continuous spray process.

Alternatively, the foams may be applied in a manner to fill orsubstantially fill a mold or fed into an extruder or an injectionmolding apparatus, such as for reaction injection molding (RIM), andused to form items such as cushions, mattresses, pillows, and toys. Forexample, a compound (e.g., a monomer or an oligomer) having thereon atleast one cyclocarbonate group, a polyfunctional amine crosslinkingagent, and a blowing agent may be mixed and applied to a mold where thecrosslinking agent reacts with the cyclocarbonate groups while theblowing agent degrades or reacts to form a gas and initiate the foamingreaction.

The foams of the present invention may be used to insulate buildingssuch as homes from temperature fluctuations outside of the building'senvelope. In addition, the foams of the present invention are preferablynon-structural foams. The foams may serve both as a conductive and aconvective thermal barrier. The foams of the present invention may alsoserve as a sealant or barrier to air infiltration by filling cracksand/or crevices in a building's roof or walls. Additionally, the foamsmay be used to form a barrier to seal cracks or crevasses around doors,windows, electric boxes, and the like. Further, the foams can be used inother applications, such as, but not limited to, insulating householdpipes, appliance insulation, and attic insulation.

Another advantage of the foams of the present invention is the safeinstallation of the foam into cavities. The foams do not release anyharmful vapors into the air when applied or sprayed. Therefore, theinventive foams reduce the threat of harm to individuals working with orlocated near the foam. In addition, the application of the foams is moreamenable to the installer as he/she will not need to wear a specialbreathing apparatus during installation.

Another advantage of the inventive foams is that it can be used in therenovation market, as well as in houses that are occupied by persons oranimals. Existing, conventional spray polyurethane foams cannot be usedin these applications because of the generation of high amounts of freeisocyanate monomers that could adversely affect the occupants of thedwelling. As discussed above, exposure of isocyanate monomers may causeirritation to the nose, throat, and lungs, difficulty in breathing, skinirritation and/or blistering, and a sensitization of the airways.

It is further advantageous that the inclusion of the plasticizer in theB-side allows for the inclusion of other solid materials that may addfunctionality and/or cost savings to the final foamed product.

It is also an advantage of the present invention is that the componentsof the two-part foam compositions are carefully chosen to result in atacky or sticky foam that can be used to hold the fiberglass batt inplace when used to fill cracks or crevasses. Such tackiness is desirablewhen flash and batt systems are employed.

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples illustrated belowwhich are provided for purposes of illustration only and are notintended to be all inclusive or limiting unless otherwise specified.

EXAMPLES Example 1

The components of Part A and Part B, indicated in Table 1, were mixedtogether in container and permitted to foam. The time from initialfoaming to the time when the foam cured and became tack free wasdetermined to be less than 2 minutes.

TABLE 1 Formulation 1 Tradename Description Gram (g) Wt Pct (%) Part ADER 331 Epoxy resin 53.12 45.73 Epon ™ 8111 multi- 18.98 16.34functional resin* NaOH (0.1N) base 0.76 0.65 Part B Cycloate A/Preformed 20.32 17.49 Ancamine 2678 oligomer Epikure ™ 3271 excesspolyamine 4.74 4.08 HFC-245a blowing agent 12.24 10.53 DC193 surfactant/5.89 5.07 plasiticizer Tint Ayd dye 0.1 0.09 Total 116.2 100.0*multifunctional resin having both epoxy and unsaturationfunctionalities

Example 2

For each of formulations 2 and 3, the respective components of Part Aand Part B, indicated in Table 2, were mixed together and sprayed on avertical cavity using an Oaks mixer.

TABLE 2 Formulations 2 and 3 Formulation 2 Formulation 3 TradenameDescription Gram (g) Pct (%) Gram (g) Pct (%) Part A D.E.R 331 Epoxyresin 847.76 51.5% 408.32 25.5%  Mcure-400 acrylate monomer 163.14  9.9%480 30.0%  FEA -1100 blowing agent 189.36 11.5% 198.4 12.4%  Garamite1958 rheology modifier — — 32 2.0% Part B Cycloate A/ Preformedoligomer* 135.47  8.2% 158.08 9.9% Ancamine 2678 Ancamine 2678 excesspolyamine 212.67 12.9% — — Epikure 3271 excess polyamine — — 196.812.3%  Dabco PM 200 nucleating agent — — 8.64 0.5% DC 193surfactant/plasticizer  97.59  5.9% 104 6.5% Garamite 1958 rheologymodifier — — 12.8 0.8% Total 1646.0   100% 1599.0 100.0% 

Formulations 2 and 3 differ primarily in the percentage of MCure-400 aswell as the absence or presence of Garamite 1958. Formulation 3, whensprayed on vertical surface, resulted in total dripping of liquid downthe wall cavity (see FIG. 2A). In contrast, Formulation 3, when sprayedon vertical surface, resulted in a closed-cell foam that did not sag andstayed in place, (See FIG. 2B). This example illustrates the importanceof the acrylate monomer and the rheology modifier.

Example 3

Four foam compositions are prepared according to the formulations 4, 5,6 and 7 shown in Table 3 below. Formulations 4-7 differ from priorformulations in using a urethane acrylate oligomer, rather than acyclocarbonate-amine preformed oligomer.

TABLE 3 Formulations 4 to 7 Formulation (weight percents) TradenameDescription No. 4 No. 5 No. 6 No. 7 Part A DER 331 Epoxy resin — —29.15% 21.59% Epon 828 Epoxy resin 28.77% 27.86% — — CN9010 UrethaneAcrylate oligomer 33.82% 32.75% 34.26% — CN975 Urethane Acrylateoligomer — — — 24.92% MCure 400 Acrylate monomer — — — 16.61% Garamite1958 Rheology modifier —  2.19% —  1.69% FEA -1100 Blowing agent 14.66%14.19% 14.85% 13.29% Part B Epikure 3271 diamine 13.53% 13.10% 13.70%16.61% Dabco PM 200 nucleating agent  0.61%  0.59%  0.62%  0.42% DC 193surfactant/plasticizer  7.33%  7.94%  7.42%  0.71% Garamite 1958 Rheologymodifier  1.29%  1.39% —  4.15% Total 100.0% 100.0% 100.0% 100.0%

For each formulation, the two parts, A and B, were mixed together in acontainer, sprayed on a vertical cavity using a two-part epoxy mixer-gunand allowed to foam. Formulations #4 and #6, having no rheology modifierin Part A showed considerable dripping or sagging, whereas formulation#5 did not. Foams 4 and 5 both produced foams having greater than 80%closed cell; the closed cell content of formulation 6 was notdetermined. Formulation 7 provided a very rapid tack-free time of about5 seconds, in a non-sagging foam.

The foregoing description of the various aspects and embodiments of thepresent invention has been presented for purposes of illustration anddescription. It is not intended to be exhaustive or all embodiments orto limit the invention to the specific aspects disclosed. Obviousmodifications or variations are possible in light of the above teachingsand such modifications and variations may well fall within the scope ofthe invention as determined by the appended claims when interpreted inaccordance with the breadth to which they are fairly, legally andequitably entitled.

1. A spray foam system comprising a urethane reactant having at leasttwo reactive functional groups other than isocyanates, the urethanereactant selected from (a) a preformed urethane prepolymer and (b) acyclocarbonate and a polyamine that react in situ to form a urethaneprepolymer adduct; a crosslinker having at least two reactive functionalgroups adapted to be rapidly crosslinked with the reactive functionalgroups of the urethane reactant to form a hybrid polyurethane,optionally with a resin polymer having further reactive functionalgroups; a blowing agent for initiating a foaming reaction; and arheology modifier; wherein the urethane reactant, the crosslinker andthe optional resin polymer are separated into at least two parts on thebasis of their reactive functional groups to prevent prematurecrosslinking until a foaming reaction is initiated.
 2. The spray foamsystem of claim 1 wherein the urethane reactant comprises a urethaneacrylate adduct.
 3. The spray foam system of claim 1 wherein theurethane reactant comprises a mixture of a cyclocarbonate and apolyamine capable of forming a cyclocarbonate-amine urethane adduct inthe presence of heat.
 4. The spray foam system of claim 3 furthercomprising an acrylate monomer reactive with the polyamine to produceinternal heat.
 5. The spray foam system of claim 1 wherein the resinpolymer comprises an epoxy polymer, curable with a polyamine, the epoxypolymer and polyamine being in separate parts initially.
 6. The sprayfoam system of claim 5, further comprising an auxiliary cros slinkingagent comprising an acrylate monomer.
 7. The spray foam system of claim1 wherein the urethane reactant comprises an aliphatic backbone.
 8. Thespray foam system of claim 1 wherein the urethane reactant comprises anaromatic backbone.
 9. The spray foam system of claim 1 wherein at leastsome of the reactive functional groups of the urethane reactant areamine reactive groups.
 10. The spray foam system of claim 1 wherein atleast some of the reactive functional groups of the urethane reactantare vinyl reactive groups.
 11. The spray foam system of claim 1 whereinthe blowing agent is a low-boiling point fluorocarbon.
 12. The sprayfoam system of claim 11 wherein the low-boiling point fluorocarbon isselected from HFC 245fa, FEA-1100 and mixtures thereof.
 13. A method ofsealing, insulating or sealing and insulating part of a buildingstructure, comprising mixing the at least two parts containing thecomponents of the spray foam system of claim 1; applying the mixture tothe building structure, thereby permitting the urethane reactant, thecrosslinker and optional resin polymer to crosslink, and initiating ablowing reaction to form a foamed product, the rheology modifier holdingthe mixture in place against the building structure for a timesufficient for the blowing agent to produce a three-dimensional,tack-free foamed product.
 14. The method of claim 13, further comprisingheating one or more of the at least two parts to a temperature aboveambient temperature prior to or at the time of application.
 15. Themethod of claim 13 further comprising delivering each of the at leasttwo parts to a spray device, blending them there, and applying them fromthe spray device.
 16. The method of claim 13 wherein the foamed productcures to tack-free status in less than about 120 seconds.
 17. The methodof claim 13 wherein the foamed product cures to resilient hardness inless than about 15 minutes.
 18. The method of claim 13 wherein the partof the building structure is a seam or crevice between two structuralcomponents.
 19. The method of claim 13 wherein the part of the buildingstructure is a cavity or open space framed by structural components. 20.The method of claim 13 wherein the blowing reaction is initiated byde-pressurization of a low-boiling point fluorocarbon.
 21. A hybridpolyurethane foamed product made by the process of: reactingnon-isocyanate reactive functional groups of a urethane reactant with acrosslinker having at least two reactive functional groups adapted to berapidly crosslinked with the reactive functional groups of the urethanereactant to form a hybrid polyurethane, optionally with a resin polymerhaving further reactive functional groups, in the presence of a rheologymodifier under conditions to rapidly form cells of a crosslinked hybridpolyurethane polymer; while initiating a blowing reaction to cause a gasto be disposed within at least some of the cells.
 22. The foamed productof claim 21 wherein the cells are at least 80% closed.
 23. The foamedproduct of claim 21 wherein the urethane reactant is selected from thosehaving an aliphatic backbone, those having an aromatic backbone, thosehaving polyesters in the backbone, and those having polyether in thebackbone.
 24. The foamed product of claim 21 further comprising an epoxyresin.
 25. The foamed product of claim 21 further comprising an acrylatemonomer.
 26. The foamed product of claim 21 wherein the blowing reactiongas is a low-boiling point fluorocarbon.